Randomly interesterified sunflower and tobaccoseed oils

ABSTRACT

The specification describes a highly nutritive margarine containing a high proportion of polyunsaturated acids. The margarine is physically stable with respect to texture at deepfreeze storage temperatures (e.g., -10*F) when at least 25 percent of the oil therein having a high polyunsaturated content has been randomly interesterified.

United States Patent McNaught Aug. 19, 1975 RANDOMLY INTERESTERIFIED 3,600,195 8/1971 Westenberg 99/122 SUNFLOWER A TOBACCOSEED OILS 3,748,348 7/1973 Sreenivasan 260/41().7

Inventor: John P. McNaught, Saddle River,

Lever Brothers Company, New York, NY.

Filed: Oct. 6, 1972 Appl. No.: 295,744

Related US. Application Data Division of Ser. No. 77,757, Oct. 2, 1970, Pat. No. 3,746,551, Continuation-impart of Ser. No. 10,313, Feb. 10, 1970, abandoned.

Assignee:

US. Cl. 260/4l0.7; 426/189; 426/194; 426/362; 426/417 Int. Cl ..C1lc 3/10 Field of Search 260/410.7; 426/189, 194

References Cited UNITED STATES PATENTS 1/1960 Melnick et a1 99/122 OTHER PUBLICATIONS Chakrabarty et al], J. Chromatography, V01. 31, pp. 556-559 (1967);

Primary Examiner-Donald G. Daus Assistant ExaminerDiana G. Rivers Allorney, Agent, or Firm-Kenneth F. Dusyn; Melvin H. Kurtz 57 ABSTRACT I 10F) when at least 25 percent of the oil therein having a high polyunsaturated content has been randomly interesterified.

2 Claims, No Drawings RANDOMLY INTERESTERIFIED SUNFLOWER AND TOBACCOSEED OILS This application is a division of application Ser.. No. 77,757, filed Oct. 2, 1970, 3,746,551, which is a continuation-in-part of application Ser. No. 10, 313, filed Feb. 10, 1970, and now abandoned.

BACKGROUND OF THE INVENTION now US. Pat. 'No.

associated with atherosclerosis, leading medical authorities to prescribe diets which include polyunsaturated fats in an effort to lower cholesterol levels.

I Many medical experts believe that there is a relationship between the intake of polyunsaturated fatty acids and the level of plasma cholesterol. It has been reported that high levels of blood cholesterol can be reduced when large amounts of vegetable fats are included in the diet, and that the level will be'increased when large amounts of animal fats are taken. The presl. Field of the Invention ent-day trend toward the use of hydrogenated oils in 'This invention relates to a margarine having a high food products leads to a lessened intake of essential polyunsaturated fatty acid (alternatively referred to fatty acids, resulting in the esterification of body chohereinafter as fatty acid or fat) content and a low satulesterol with saturated fatty acids. These esters are not rated fatty acid content and which is physically stable l5 readily disposed of by the body, nor are phospholipids with respect to texture change at deep-freeze storage containing saturated fatty acids, but are retained to a temperatures, e.g., 10F. Such stabilityis achieved by great degree in the plasma. They may cause atheroma, employing in the margarine randomly interesterifiedoil a disease characterized. by fatty degeneration of the having at least 65 percent polyunsaturated fatty acids, inner coat of the arteries, and may increase the coaguas more fully set forth hereinafter. lability of the blood, and contribute to coronary and ce- It is well known that the natural glyceridic oils and rebral thrombosis. fats are mixtures comprising glyceryl esters of fatty An elaboration of the effects of polyunsaturated fatty acids having different chain lengths and different deacids in the body may be found in Lipids by H]. Degrees of unsaturation. uel, Jr., Vol. III, 1957, pps, 800-834.

In recent years, nutritionists and medical 'practitio- Arachidonic acid occurs .to some extent in marine ners have become increasingly aware of the dietary imoils, although these oils are not considered suitable for portance of polyunsaturated fats. The polyunsaturated use in margarine without hydrogenation. The acid ocfatty acids are, according to authorities, a dietary recurs only .in very smalal amounts, in animal fats, and for quirement for protection against fat-deficiency sympall practical purposes not at all in vegeable oils. Thus it toms. Linoleic, linolenic, and arachidonic acids have is impractical to attempt to introduce a high arachibeen recognized as the chief polyunsaturated fatty donic acid content into a food product by the incorporacids which possess an appreciable biopotency in counation of a naturally occurring fat therein. This acid teracting fat deficiency. however is synthesized in the body by conversion from Linoleic, linolenic, and arachidonic acids are linoleic acid. Linoleic and linolenic acids are not synstraight-chain aliphatic monocarhoxylic acids, referred thesized in the body and must be taken in the diet. to in the art as fatty acids, which occur in nature com- Linoleic acid, usually along with small amounts of bined as esters with glycerol. They have two, three, and linolenic acids occurs at a relatively high level comfour olefinic double bonds respectively in their molecubined as glycerides in a great number of well-knownedlar structure, and may be represented as follows: 0 ible vegetable oils, for example safflower, tobaccoseed,

Linoleic acid: 9. 12,-octadecadienoic acid It willbe recognized that the fatty acid percentages shown in the table are re arded as t ical onl and that CH=*(CH2)CH=CHCH2CH:CH(CH2)7COOH the percentages may var y with clirii te and geographi- Linolenic acid: 9, 12 15-octadecatrienoic acid cal location. 1 v

Within this group of oils, those havin percent or CH=*(CH2)4CH=CHCHZCHZCHCH2CHZCHCH2CH- more polyunsaturated fatty acids are wi thin the instant :CH(CH2)3COOH invention. Normally these will be safflower and tobac- Arachidonic acid: 5, 8, 1 1, l4-eicosatetraenoic acid co'seed oils, although any triglyceride oils of which spe- Polyunsaturated acids of the type described above 50 cial high-linoleic acid-varieties may be grown are suitare believed to be required for growth and for the able provided that they can be formulated with a hard maintenance of normal skin conditions by a wide varistock to provide a margarine having a ratio of polyunety of animals, including man. These fatty acids medisaturated acid to saturated acid of at least about 3.5 to ate not only growth but also certain diverse functions 1. v r such as protection from x-irradiation injury, mainte- 5 Sunflower oil is an example of an oil having one or nance of capillary resistance in the skin capillaries, and more varieties with a higher linoleic acid content than the normal transport and metabolism of cholesterol; I does the conventional variety having. the analysis Abnormally high blood cholesterol levels have been shown in TABLE 1 TYPlCAL COMPOSITIONS OF SOME SELECTED OILS Bailey's industrial Oil and Fat Products. Third Ed, lntcrscience Publishers, 1964 Fatty Acid C otton- Hcmp Lin Pca- Saf- Sun Rape- Mustard- Tobacco- Tea- Corn seed secd seed Olive Palm nut flower flower Sesame seed seed seed seed Total saturated I7 24 8 l() 16 53 17 l 1 l5 l7 l5 6 5 l l 9 Unsaturated: 4

( and lower 2 r Olcic m] Z9 Z5 12 22 64 38 61 13 25 29 4U 19 22 14 80 Linoleic um 54 51 5 l6 l6 9 22 51 52 43 l4 I5 75 ll TABLE l-continued TYPICAL COMPOSITIONS OF SOME SELECTED OILS Bailey's Industrial Oil and Fat Products. 'Ihird Ed. lntcrscience Publishers, 1964 Fatty Acid Cotton Hempl.in- Pea- Saf- Sun Rupe- Mustard- Tohacco- Tea- Corn seed seed seed ()livc Palm nut flower flower Sesame seed seed seed seed Linolcnic C 25 52 2 l 9 2 Z 8 7 Eicoscnoic C n 7 Erucic C 40 44 The figures are those obtained by GLC analysis where available. Some figures are selected as "most probable within a given range.

table I. Varieties are known having 65 percent or more linoleic acid.

It is not within the ambit of the present invention to have for an object the alleviation of fat-deficiency symptoms, nor is there any representation that the product of the invention has curative properties. However there has been discovered a way to provide those who wish to use a margarine containing a high level of polyunsaturated fatty acids with a product that is texture stable at deep-freeze storage temperatures such as minus 10F as explained in detail hereinafter.

Safflower oil and other polyunsaturated fats are currently marketed as salad oils, and persons desiring to enrich their intake of polyunsaturated fats can avail themselves of 'these products. It is evident that there is a need for other edible products containing high proportions of polyunsaturated fatty acids to enlarge the scope of availability of such products to persons desiring to increase their intake of polyunsaturated fatty acids.

One of the most popular foods is margarine, which is a food consumed in large quantities, and by people of all agess. Margarine contains at least 80 percent aleaginous matter (imitation margarines contain substantially less), and in view of its widespread use, is a particularly suitable product for the incorporation of an-oil having at least 65 percent polyunsaturated fatty acids.

In order to introduce as much polyunsaturated fatty acids, relative to the saturated fatty acids, as possible into the diet through the use of margarine, the liquid oil fraction of the margarine will be non-hydrogenated and will advantageously be an oil that contains the highest proportion of polyunsaturated acids combined as triglycerides.

Safflower oil is available in commercial quantities and has the highest linoleic acid content of the vegetable oils available in large volume, and for this reason is the preferred oil for use to provide the highest possible polyunsaturated acid content and the lowest saturated fatty acid content.

However when safflower oil or other oil having at least 65% polyunsaturated acids is used, the margarine has a serious defect in that when it is stored under deep-freeze conditions, e. g., about lF. to about -i F., it is physically unstable, that is, the margarine texture breaks down and develops a granular, lumpy appearance, accompanied by loss of body, making the product unsightly and unsalable.

The Prior Art Much of the early work done on the intcresterification of fats and oils is found in patents to Eckcy, as for example in US. Pat. Nos. 2,442,531. 2,442,532, and 2,442,536. These patents are concerned with directed interesterification and are therefore only generally relevant to the instant invention.

So far as is known, no one has encountered the problem of texture instability of margarine at deep-freeze temperature prior to the instant invention, presumably because no one has heretofore attempted to prepare a margarine having the high polyunsaturated content possible through the instant invention.

A different problem was recognized by Selden, that is, the problem of oiling-off, or the seeping of oil from margarine at temperatures above F. In US. Pat. No. 3,353,964, Seldon teaches that this problem can be solved by using in the margarine a corandomized blend of coconut oil and substantially completely hydrogenated rapeseed oil, offering the theory that the saturated C and C acids in the corandomized blend provides stiffening power which improves the heat stability of the margarine, while the C to C acids from the coconut oil on the same molecule as the long-chain acids reduces the melting point of the glyceride.

Other investigators have used corandomized blends of safflower oil and other oils in margarine. In each instance the proportion of polyunsaturated fatty acids has been lowered by the introducton of saturated fatty acids in the blend. For example US. Pat. No. 2,855,31] to Nelson describes a corandomized blend of safflower oil and lard. US. Pat. No. 3,268,340 to Babayan discloses a corandomized blend of safflower oil and a high-lauric oil such as coconut oil.

The preparation of a margarine having a high essential fatty acid content from a corandomized blend of a hydrogenated fat and an oil of high polyunsaturated content is described by Melnick in U.S. Pat. No. 2,921,855. This patent is concerned with a margarine having generally a higher saturated acid content than the margarine of the instant invention, and consequently a lower ratio of polyunsaturated-to-saturated acids, without the texture problem at deep-freeze temperatures.

Still other investigators have reported on the fatty acid distribution of safflower oil. Scholfield and Dutton in J.A.O.C.S. 35 493496 (October 1958) describe experiments from which they conclude that natural safflower oil has a random configuration.

Gunstone and Qureshi in .I.A.O.C.S. 42 961-965 1965) present data which show that linoleic acid occurs on the 2-carbon (beta carbon) of glycerol in safflower oil more frequently than would by the case under random distribution. It was concluded by these authors that the fatty acids in safflower oil are not randomly distributed with respect to alphabeta position- SUMMARY OF THE INVENTION It has now been discovered that the problem of instability of margarine having a high content of polyunsaturated fatty acids at deep-freeze temperatures can be alleviated by employing oil that has been randomly intercsterified.

SChOlflCld and Duttons conclusion that natural safflower oil has random configuration appears to be at variance with the instant finding that randomization of natural safflower oil changes its properties in margarine with respect to texture stability at deepfreeze temperatures. This change in property, i.e., texture stability at deep-freeze temperatures, is a property on which the present invention is predicated, and since the margarine is unstable when natural safflower oil (or other oil having at least 65 percent polyunsaturated fatty acids) is used, by texture-stable when the oil is subjected to a randomization process, it becomes clear that the randomizing process causes a change in structure.

Accordingly it is an object of the invention to prevent adverse texture change in a margarine having a hard stock component and a liquid oil component with at leastt 65% polyunsaturated fatty acids, by employing as the said liquid oil component one that has been at least partially randomly interesterified.

It is another object of the invention to provide a margarine having a content of polyunsaturated fatty acid of about 62 to about 70 percent, based on the total fatty acids content, and wich does not undergo adverse texture change over prolonged periods of storage at l0to F.

It is still another object of the invention to provide a margarine having a high content of polyunsaturated fatty acids, which is stable for prolonged periods at l0 to l5 F., and which contains hard stock that is not corandomized with the liquid stock thereby retaining the fa] l bodying and stiffening effect of the hard stock.

These and other objects of the invention are accomplished by incorporating into the non-hydrogenated liquid stock a randomly interesterified safflower oil or other oil of high polyunsaturated content as a part or all of the liquid stock.

In the practice of the instant invention the liquid oil component may be a single oil having a polyunsaturated fatty acid content of at least about 65 percent, or a mixture of such oils. The liquid oil component may also contain a minor proportion of oils having a polyunsaturated content slightly lower than about 65 percent, for example from about 50 to about 65%, provided that the margarine made therefrom, having both liquid and hard stock components, has a polyunsaturated-tosaturated fatty acid ratio within the range of about 3.5 to l to about 5 to 1. To correct the texture problem under deep-freeze conditions the higher polyunsaturated content oil or mixture may be randomized alone or may be mixed with the lower polyunsaturated content oil before randomizing provided that at last percent of the higher polyunsaturated content oil is randomized.

ln ins broadest aspect, the invention comprises a margarine having about 80 to about 95 percent of a glyceridic aleagenous mixture and the balance an aqueous phase, said aleaginous mixture containing about 80 to about 94 percent of a non-hydrogenated glyceride oil having a major proportion of a triglyceride component with a polyunsaturated fatty acid content of at least 65 percent which is at least 25 percent randomly interesterificd, said hard stock comprising triglycerides having an iodine value between about 35 and 60 and a saturated fatty acid content of between about 25 and 60 percent of the total fatty acids, the ratio of polyunsaturated fatty acids to saturated fatty acids in said ole- 6 aginous mixture being from about 3.5 to l to about 5 to 1.

As a preferred embodiment, the invention comprises a margarine having about percent of a glyceridic aleaginous mixture and about 20 percent aqueous phase, said mixture containing about 80 to 94 percent non-hydrogenated safflower oil and the remainder a hard stock and ,minor additives, said safflower oil consisting essentially of a member of a group consisting of randomly interesterified safflower oil and a mixture of at least about 25 percent randomly interesterified safflower oil and the balance non-interesterified safflower oil, said hard stock comprising triglycerides having an iodine value between about 35 and 60 and a saturated fatty acid content of between about 25 and 60 percent of the total fatty acids.

The expressions oleaginous mixture and alternatively glyceridic oleaginous mixture are intended herein to refer to the total mixtures of oils and fats, both saturated and unsaturated, contained in the margarines of the invention and includes the minor additives solubilized in the oils and fats such as stabilizers, preservatives, and the like.

The naturally occurring glycerides comprise predominantly triesters, the molecules of which have a glyceryl radical combined with three fatty acid acyl radicals.

The triesters are often referred to as triglycerides, and the partial esters, i.e., monoand diesters, are referred to as monoglycerides and diglycerides, respectively.

The term total fatty acids is well known in the fats and oil art to refer to the amount of fatty acids that can be obtained from a fat or oil by hydrolysis or alkaline saponification, followed by solvent extraction or other separation from an acid aqueous medium.

When reference is made in the specification and claims to the percentage of polyunsaturated of saturated fatty acid content of an oil, it will be understood that the percentage is calculated on the basis of the total fatty acid content.

The unqualified term oil" as used throughout this specification and claims refers to glycerides that are pourable at room temperature (about 25C.), and more particularly to the pourable oils composed principally of triglycerides, either natural, or synthesized for example by reacting glycerol or a partial glyceride with a natural or synthetic fatty acid.

By random interesterification is meant the interchange of fatty acid radicals on the glyceryl radicals in random fashion. ,The interchange continues dynamically when the oil is in the liquid state under the influence of a catalyst, until the mixture of molecular configurations reaches an equilibrium in accordance with the laws of probability. The term molecular configuration refers to the identity of the three fatty acid, or acyl (RC=O) radicals combined with one glyceryl radical. All three fatty acid radicals in some molecules will be saturated, and in others unsaturated, either of the same chain length or of differing chain lengths. In other molecules, there will be two saturated and one unsaturated fatty acid radicals and in still others this pattern will be reversed, the several chain lenghths being randomly distributed. The overall combined fatty acid distribution with respect to chain length and degree of unsaturation is not altered by the random interesterification process. Molecules of glycerides having mixed combined fatty acid radicals will include those known as, for example, trilinolein, dilinolein monoolein,

dilinolein monostearin, tristcarin, distearin-monoolein, distearin-monopalmitin, monostearin diolein, dimyristin-monoolein, triolein, etc. Thus RC in the acyl radical RC= shown above may be a saturated hydrocarbon radical such as C H C H C H C d-1 C d-1 or the corresponding monoor polyunsaturated radicals. The natural oils do not contain important proportions of unsaturated radicals having chain lenghts under C Randomization as understood to take place for use in the invention includes random positioning of the fatty acid radicals within a triglyceride molecule with respect to alpha-beta positioning, as well as random distribution of the fatty acids among the glycerol molecules. The randomized mixture will contain for example:

a. alpha-alpha-distearin-beta-monoolein b. alpha-alpha dilinolein-beta-monoolein c. alpha-monostearin-alpha monopalmitin-betalinolein d. alpha-alpha-dilinolein-beta monomyristin e. alpha-beta dilinolenin, alpha monopalmitin f. trilinolein Those skilled in the art will know all the possible configurations, only a few of which are set forth above.

The molar precentage of the trisaturated, triunsaturated, and mixed saturated-unsaturated molecules. leaviing out of consideration the varying molecular weights of the mixed fatty acids and the possible positional isomers, may be calculated by the following for mula, based on the formula found in Bailey, Industrial Oil and Fat Product Second Ed., 1951, lnterseience Publishers, Inc., pagee 834.

% trisaturated (s) X l/l0,000

% disaturated-monounsaturated 3 X (s)- l/l0,000 X 70 diunsaturated-monosaturated 3 X s X (H) X l/ 10,000 E x triunsaturated (0) X 1/l0,000 wherein s: the molar percentage of saturated acids n the molar percentage of unsaturated acids and In the randomizing process, any of the recognized alkaline catalysts, such as a sodium alkoxide having from 1 to about 4 carbon atoms, sodium metal, sodiumpotassium alloy, sodium hydroxide, etc. may be used. A sodium alkoxide is preferred. The process may be carried out at temperatures as high as about 150C. and as low as about C., so long as the oil remains liquid. Usually it is not necessary to use a temperature outside of the range of about 50to 100C, and within this range a temperature of about 70C. is commonly used. Processing time is usually /2to 1 hour.

It is theorized that the stability obtained through the use of randomized safflower oil is due to the slight increase in the content of trisaturated and disaturated molecules, along with possibly some alpha-beta shifting, to produce crystal matrices that are less subject to phase changes with slight temperature fluctuations under deep-freeze conditions.

The attributing of the excellent stability resulting from the instant invention to the increase in diand trisaturated molecules as discussed immediately hereinabove, is set forth as a theory, to which however it is not desired to be held.

It is a part of the invention advance of the instant invention that the increase in disaturated-monounsaturated and trisaturated molecules is accomplished without lowering the proportion of polyunsaturated acids.

It has been observed, as shown below in Example 1, that when the entire amount ofsafflower oil used is randomized, the margarine made therefrom is stable at minus 10F., but exhibits slight emulsion instability when stored at room temperature for several days. However when the same amount of non-randomized safflower oil is used, the margarine is texturally unstable at minus 10F., but the emulsion is considerably more stable at room temperature.

The emulsion instability can be demonstrated by disturbing the surface of the margarine such as by cutting or scraping, whereupon some liquid oil collects at the disturbed area.

In the normal channels of commerce, the margarine is desirably stored under deep-freeze conditions for relatively long periods of time, while once in the hands of the consumer, the time during which the margarine would be exposed to room temperature conditions is relatively short, consequently protection of the margarine at deep-freeze temperatures is of prime importance.

The margarine contemplated within the instant invention preferably is the type that has become increasingly popular in the past few years, referred to as soft margarine. This margarine is only slightly softer than the conventional print margarine, but too soft to withstand commercial handling if packaged in print form. Consequently the soft type margarine is packaged in tubs, or small containers, usually made of plastic, and which are sometimes decorated for a more attractive appearance.

The solid fat index (SFl) of the margarine is somewhat lower than conventional print margarines due to the high content of liquid oleaginous ingredients. The margarine of the invention has the following range of SFl values:

about 2.6 to 9 at 32F.

about 1.8 to 6 at F.

about 0.4 to 3.5 at 92F.

about 0 to 1.0 at 104F.

The softness of the margarine of the invention may be judged by a comparison of penetrometer readings and solid fat indexes (SFI) of a margarine within the invention (Example 3 and of conventional print margarines and butters. These characteristics are set forth in table [1 below.

TABLE ll Penetration SFl 45F. 70F. 32F. 70F. 92F.

Margarine of 230 343 6.4 4.2 L7

Print Margarincs l00-l30 230-300 l9-2l l l.7l4 3.5 max Butters 35-76 13 3-300 9 1 mm. The number of tenths of a millimeter which the cone penetrates below the surface is recorded as the penetration.

The solid fat index (SFl) is calculated from dilatometer measurements as described in AOCS Tentative Method Cd 10-57 (1961 The margarine of the instant invention may be prepared by any conventional process. By way of general description, the process comprises randomly interesterifying a glyeeride oil which preferably has been refined and bleached and which has a polyunsaturated fatty acid content of at least 65 percent, based on the weight of the total fatty acids, then with or without the addition of nonrandomized glyceride oil having a polyunsaturated fatty acid content of at least 50 percent, blending in a hard stock having the characteristics hereinafter defined, subjecting the blend optionally to a refining process, then to a deodorizing process, followed by mixing in an edible emulsifier, such as monoand diglycerides, lecithin, or sodium monostearin sulfoacetate, and if desired, colorants (carotene) and vitamins. The oleaginous mixture of oil, hard stock, emulsifier, and optionally, colorant and vitamins, is emulsified with an aqueous phase to form a water-in-oil emulsion at a temperature at which the oleaginous mixture is liquid, preferably about 4042C. The water usually but not necessarily, has dissolved therein one or more of the substances listed in table lll. Skim milk may be used in place of water. The emulsion is pumped through a scraped-surface heat exchanger such as a Votator, a description of which is found in Industrial Oil and Fat Products, Bailey 3rd ed., p. 1066, lnterscience Publishers, Inc. 1964. lf a slightly aerated product is desired, a gas such as nitrogen or air is introduced into the emulsion prior to reaching the heat exchanger. The emulsion is supercooled in the Votator and leaves the A unit in a substantially liquid state. It is then passed through the B unit (mixer) with release of pressure if the gas has been incorporated, and a change in state of the gas from solution to occlusion while the fat is crystallizing. The margarine leaving the B unit is run into containers, serving as molds, and tempered to solidify into a firm, shaped mass. Preferably the tempering is carried at a temperature of about 7C. to about 10C. and for a time of about 24 hours, but may be carried out at room temperature if desired.

Federal Standards of Identity require that margarine contain at least 80 percent fat (herein oleaginous mix ture). Accordingly a preferred food product of the present invention comprises a margarine having at least 80 percent fat, the balance being an aqueous phase. The benefits of the invention are realized when the fat content is about 80 to about 95 percent and even below this range.

The content of polyunsaturated fatty acids will be from about 60 to about 75 percent. Although the polyunsaturated fatty acid may be somewhat lower, for example, about 58%, it will be understood that the instant invention is of greatest benefit when the polyunsaturated fatty acid content is in the upper region of a practical range, for example about 60 to about 75 percent, and preferable from about 64 to about 70 percent, based on the weight of the oleaginous mixture.

The non-hydrogenated glyeeride oils necessary for the practice of the instant invention have a linoleic acid content of about 65 to about 79 percent, and a saturated fatty acid content substantially all palmitic and lodine Value Palmitie Acid 7.] percent Stearic Acid 29 percent Oleic Acid 14.0 percent Linoleic Acid 75.5 percent Linolenic Acid 02 percent Other Acids, Saturated 0.2 percent Other Acids, Unsaturated 0.1 percent Solid Fat Index 0 at 0C.

The acids listed above are of course present as glycerides.

Throughout the specification, figures representing percentage of fatty acids in an oil are percentages based on the total fatty acid content of the oil.

The molecular configuration before randomization with respect to saturated acids, oleic acid and linoleic acid, is as follows:

oleicsaturated-saturated linoleic-saturated saturated 2 oleic-olcic-saturatcd l linoleic-oleic-saturatcd 7 linoleielinoleic-saturated l8 oleiooleic-oleic l linoleic-oleic-oleic 5 linoleiclinoleic-oleic l9 linoleic-linoleic-linoleic 47 Expressed in terms of molar percentage of saturated and unsaturated fatty acids, the structure before and after randomization is as follows:

Before After trisaturated None 0. l disaturated 2 3,5 monosaturated 26 239 tri-unsaturatcd 72 72.5

The hard stock may be any glyeeride oil or mixture thereof characterized by an iodine value between about 35 and about 60, and preferably between about 40 and about 55, and by a saturated acid content of between about 25 and about 60 percent, preferably between about 33 percent and about 53%, based on the total fatty acid content. Suitable hard stocks are partially hydrogenated rapeseed oil having an iodine value' 'of 53-55, a 50/50 mixture of cottonseed winter oil stearine and peanut oil having an iodine value of 4050, or partially hydrogenated cottonseed, soybean, peanut, corn, safflower, or mustardseed oils or mixtures of the above, having iodine values between about 35 and about 60. In general, the higher the proportion of hard stock in the margarine, the higher the iodine value should be within the above-mentioned range.

Cottonseed winter oil stearine is the term applied to the solid fraction from the Winterizing of cottonseed oil. In a Winterizing process, the oil is chilled for example to about 45to 50F. and the solid components allowed to crystallize over a period of time. The solid fraction is then separated from the liquid fraction. The solid fraction or stearine contains some entrapped liquid oil, the amount being variable from batch to batch. The iodine value (I.V.) of the stearine is usually between 75 and 100.

The expression aqueous phase herein refers to water or to water with the usual water soluble additives (see table III below) solubilized therein, which is the minor phase of the water-in-oil emulsions (margarines) of the invention.

The aqueous phase may contain water, salt, potassium sorbate, flavor, ground soybean, or milk in the form of whole milk, cream, skim milk, or reconstituted skim milk.

Some suitable compositions for the aqueous phase are set forth in table 111. The figures are parts by weight, unless otherwise noted.

"' to a total of 19.7 to 20 pans "disedium calcium ethylenediaminetetraacetate The invention will be more fully understood in view of the detailed description set forth in the Examples which follow, which are illustrative but not limitative of the invention.

EXAMPLE 1 Safflower oil is randomized by the following procedure.

800 to 1000 lbs. of safflower oil is pumped into a tank fitted with a jacket, a stirrer, an evacuating system, and a draw-off valve. The oil is refined by alkali treatment, and then dried for one hour at 150C. The oil is cooled with stirring at about 70C. and 0.2 percent sodium methoxide powder added, and the oil stirred for an additional hour at 70C., under a nitrogen blanket, whereupon the oil becomes interesterified in random configuration, as disclosed elsewhere herein. The process is conducted ,under a nitrogen blanket to inhibit oxidation.

After randomizing, the oil is washed with water to inactivate the catalyst and to remove alkaline substances, e.g., sodium hydroxide and soaps, derived from the sodium methoxide catalyst, then refined, bleached, aand deodorized.

For the preparation of a margarine, 90 parts by weight of the safflower oil treated as above and parts by weight of 42.3 I.V. 50/50 blend of peanut oil and cottonseed winter oil stearine having a saturated fatty acid content of 53 percent are weighed into a churn at about 55C. and a monoglyceride made from 82 IV.

1 2 cottonseed oil added, along with lecithin, vitamin A, and carotene.

Into a separate tank is placed nonfat dry skim milk which is reconstituted with 10 parts water, pasteurized, and cooled to 40F. About one-tenth of this milk product is cultured and returned to the tank. Salt, potassium sorbate, and flavor are then added. Nineteen and eighttenths parts by weight of this aqueous mixture are blended with 80.2 parts by weight of the oil to form a water-in-oil emulsion. The temperature of the emulsion is adjusted to 4042C. and fed at the rate of 220 pounds per hour through a scraped-surface heat exchanger after dissolving suffieient nitrogen gas (l2%14% by volume) under pressure to provide the desired specific gravity to the margarine. The margarine is run in a semifluid state into 8-ounce containers at a temperature of about l4l5C. and held at about 7C. until firm.

The composition of the margarine is as follows:

Oleaginous Mixture Parts by Weight Glycerides 79.794 Mono/diglycen'de emulsifier 0.18 Lecithin 0.22 Vitamin A and beta-carotene 0.006

Aqueous Phase Parts by Weight Reconstituted skim milk 17.924

(9.1% solids) Salt 1.75 Potassium sorbate 0.10 Flavor 0.026

The polyunsaturated content is 68.1 percent and the saturated acid content is 14.5 percent, based on the total of safflower oil and hard stock. The penetration is 235 at 45F. and 402 at F. The ratio of polyunsatu rated acids to saturated acids is 4.7.

The margarine is stored at minus 10F. for 26 weeks. At the end of this time the texture is smooth. When stored at room temperature it is observed that the emulsion exhibited some instability as evidenced by the appearance of some free oil in a cavity formed by removing some of the margarine from the surface. This indicates a limited storage stability at room temperatlll'fi.

EXAMPLE 2 For economic reasons, it will be advisable to admix as much non-randomized safflower oil with the randomized oil as the system will tolerate. Table IV, below shows the textural stability is improved when the proportion of randomized oil is as low as 25 percent of the total liquid oil. Experiments performed to determine the stability of margarine in which the ratios of randomized to non-randomized safflower oil are 50/50, 35/65, and 25/75, in addition to ratios of /0 and 0/100 provide stability data, after storage at minus 10F., in terms of the development of a lumpy, granular texture, which are given in Table IV. A particularly preferred product is one in which about 50 percent of the liquid oil is randomized. At this blend, the texture and body after storage at minus 10F. are satisfactory, and the free oil formation at room temperature is minimal.

TABLE IV Ratio of Randomized to Non-Randomized 7? Composition Safflower Hard of Hard Penetration Textural Stability Oil Stock Stock 45F. 70F. 1 week 4 weeks 6 weeks 12 weeks 26 weeks 100/0 10 43.3 l.V. 235 402 S S S S S 50/ 50 CSWOS and peanut oil 50/50 10 250 372 S S S S 35/65 10.75 49.7 [.V. 248 367 S S 5 S 50/50 CSWOS and peanut oil 25/75 10.75 255 389 S U 0/100 43.3 l.V. 223 398 U 50/50 CSWOS and peanut oil CSWOS cottonseed winter oil stearine U unstzihlcdumpy. granular texture and loss of body in less than one week S stable-smooth texture S" believed to be stable for longer periods, but no observations were made beyond the time indicated U"" stable for more than 2 weeks but less than 4 weeks EXAMPLE 6 EXAMPLE 3 A margarine is made as described in Example 1 except that the glycerides are composed of 44.625 percent randomized safflower oil, 44.625 percent non-randomized safflower oil, and 10.75 percent of a mixture of equal parts of cottonseed winter oil stearine and peanut oil having an iodine value of41.6, and SP1 values of 71.5 at 21.1C., 62.6 at 33.3C., and 41.7 at 40C., and a saturated fatty acid content of 52.1 percent. The texture of the margarine does not change after storing more than 4 weeks at minus 10F. The penetration at 45F. is 230 and at 70F. is 343. The polyunsaturated to saturated fatty acid ratio is 4.6.

EXAMPLE 4 A margarine is made by the process of Example 1 except that the glycerides are composed of 88.5 percent randomized safflower oil and 11.5 percent hard stock composed of a 50/50 blend of cottonsed winter oil stearine and peanut oil, this hard stock blend having an iodine value of 42.3, and a saturated fatty acid content of 53 percent.

The margarine has a penetration of 231 at 45F. and 339 at 70F. lt is still texturally stable upon examination after 13 weeks storage at minus 10F. lts polyunsaturated oil content is 67 percent, based on the total of safflower oil and hard stock.

EXAMPLE .5

A margarine is made by the process of Example 1 ex cept that the glycerides are composed of 85 percent randomized safflower oil and 15% hard stock composed of rapeseed oil hardened to an iodine value of 54.7. The saturated fatty acid content of the hard stock is 33 percent.

The margarine has a penetration of 195 at 45F. and 335 at 70F. Its polyunsaturated fatty acid content is 64.4 percent, based on the total of safflower oil and hard stock. The ratio of polyunsaturated fatty acids to saturated fatty acids is 4.7. The margarine is texturally stable after 13 weeks storage at minus 10F.

' with 40 parts of sunflower oil in which 52 percent of its Commercial margarines prepared as described herein have a polyunsaturated to saturated fatty acid ratio not greater than aboutS to l for acceptable body at room temperature, although the benefits with respect to textural stability accruing from randomization iin accordance with the invention may be noted in softer margarines having a somewhat higher ratio, for example about'6 to 1, as exemplified in Example 6.

A margarine is prepared by the process of Example 1 except that the glycerides are composed of 92 percent randomized safflower oil and 8 percent rapeseed oil hyv fatty acids is linoleic acid, 1 percent is linolenic acid and 10.0 percent are saturated fatty acids are'blended fatty acids is linoleic acid, 2 percent linolenic acid and 17 percent are saturated fatty acids. The blend is randomly interesterified by the procedure described in Example 1.

Ninety parts of the above interesterified blend and '10 parts of a hard'stock comprising a 49-1.V. blend of equal parts by weight of cottonseed winter oil stearine and peanut oil are mixed together and a margarine made therefrom in accordance with the method set forth in Example 1. The hard stock has no polyunsaturates and has 43% saturated fatty acids. The ratio of polyunsaturated to saturated acids in the margarine is 3.7 to 1.

EXAMPLE 8 Following is an example of a margarine utilizing a high-linoleic acid type sunflower oil.

Ninety parts of a sunflower oil wherein the fatty acids contain 70.4 percent linoleic acid and 12.3 percent saturated acids are randomly interesterified in accordance with the procedure of Example 1. To this are added parts of a hard stock comprising a 49 l.V. blend of equal parts of cottonseed winter oil stearine and peanut oil wherein the fatty acids contain no polyunsaturates and have 43 percent saturated fatty acids. The mixture is processed into margarine by the method described in Example 1. The linoleic acid content of the oleaginous mixture of the margarine is 63.4 percent and the saturated fatty acid content is 15.4 percent, to give a ratio of 4.1 to 1.

Having thus described the invention, the modifications thereof falling within the invention will be apparent to those skilled in the art, and the invention is to be limited only by the scope of the appended claims.

What is claimed is:

1. As a new component for margarine having a high polyunsaturated fatty acid content, randomly interesterified tobaccoseed oil wherein the fatty acids that can be obtained therefrom by hydrolysis or alkaline saponification followed by separation from an aqueous medium, have a polyunsaturated fatty acid content of at least percent, based on the total fatty acid content.

2. As a new component for margarine having a high polyunsaturated fatty acid content, randomly interesterified sunflower oil wherein the fatty acids that can be obtained therefrom by hydrolysis or alkaline saponification followed by separation from an aqueous me dium, have a polyunsaturated fatty acid content of at least 65 percent, based on the total fatty acid content, 

1. AS A NEW COMPONENT FOR MARGARINE HAVING A HIGH POLYUNSATURATED FATTY ACID CONTENT, RANDOMLY INTERSETRIFIED TOBACCOSEED OIL WHEREIN THE FATTY ACIDS THAT CAN BE OBTAINED THEREFROM BY HYDROLYSIS OF ALKALINE SAPONIFICATION FOLLOWED BY SEPARATION FROM AN AQUEOUS MEDIUM, HAVE A POLYUNSATURATED FATTY ACID CONTENT OF AT LEAST 65 PERCENT, BASED ON THE TOTAL FATTY ACID CONTENT. 2 AS A NEW COMPONENT FOR MARGARINE HAVING A HIGH POLYUNSATURATED FATTY ACID CONTENT, RANDOMLY INTERESTERIFIED SUNFLOWER OIL WHEREIN THE FATTY ACIDS THAT CAN BE OBTAINED THEREFROM BY HYDROLYSIS OR ALKALINE SAPONIFICATION FOLLOWED BY SEPARATION FROM AN AQUEOUS MEDIUM, HAVE A POLYUNSATURATED FATTY ACID CONTENT OF AT LEAST 65 PERCENT, BASED ON THE TOTAL FATTY ACID CONTENT. 